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BORN-HABER

CYCLES
A guide for A level students
KNOCKHARDY PUBLISHING
2008
SPECIFICATIONS
BORN-HABER CYCLES
INTRODUCTION
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BORN-HABER CYCLES
CONTENTS
Lattice Enthalpy
Definition of enthalpy changes
Born-Haber cycle for sodium chloride
Calculation of Lattice Enthalpy
Born-Haber cycle for magnesium chloride
THERE ARE TWO DEFINITIONS OF LATTICE ENTHALPY
1. Lattice Formation Enthalpy
The enthalpy change when ONE MOLE of an ionic lattice
is formed from its isolated gaseous ions.
Example Na
+
(g) + Cl(g) Na
+
Cl(s)
Lattice Enthalpy Definition(s)
2. Lattice Dissociation Enthalpy
The enthalpy change when ONE MOLE of an ionic lattice
dissociates into isolated gaseous ions.
Example Na
+
Cl(s) Na
+
(g) + Cl(g)
MAKE SURE YOU CHECK WHICH IS BEING USED
1. Lattice Formation Enthalpy
The enthalpy change when ONE MOLE of an ionic lattice
is formed from its isolated gaseous ions.
Values highly EXOTHERMIC
strong electrostatic attraction between oppositely charged ions
a lot of energy is released as the bond is formed
relative values are governed by the charge density of the ions.
Example Na
+
(g) + Cl(g) Na
+
Cl(s)
Lattice Enthalpy Definition(s)
NaCl(s)
Na
+
(g) + Cl

(g)
Lattice Enthalpy Definition(s)
2. Lattice Dissociation Enthalpy
The enthalpy change when ONE MOLE of an ionic lattice
dissociates into isolated gaseous ions.
Values highly ENDOTHERMIC
strong electrostatic attraction between oppositely charged ions
a lot of energy must be put in to overcome the attraction
relative values are governed by the charge density of the ions.
Example Na
+
Cl(s) Na
+
(g) + Cl(g)
NaCl(s)
Na
+
(g) + Cl

(g)
Calculating Lattice Enthalpy
SPECIAL POINTS
you CANNOT MEASURE LATTICE ENTHALPY DIRECTLY
it is CALCULATED USING A BORN-HABER CYCLE
Calculating Lattice Enthalpy
SPECIAL POINTS
you CANNOT MEASURE LATTICE ENTHALPY DIRECTLY
it is CALCULATED USING A BORN-HABER CYCLE
greater charge
densities of ions = greater attraction
= larger lattice enthalpy
Calculating Lattice Enthalpy
SPECIAL POINTS
you CANNOT MEASURE LATTICE ENTHALPY DIRECTLY
it is CALCULATED USING A BORN-HABER CYCLE
greater charge
densities of ions = greater attraction
= larger lattice enthalpy
Effects
Melting point the higher the lattice enthalpy,
the higher the melting point of an ionic compound
Solubility solubility of ionic compounds is affected by the relative
values of Lattice and Hydration Enthalpies
Cl Br F O
2-
Na
+
-780 -742 -918 -2478
K
+
-711 -679 -817 -2232
Rb
+
-685 -656 -783
Mg
2+
-2256 -3791
Ca
2+
-2259
Lattice Enthalpy Values
Smaller ions will have a greater attraction for each other because of their
higher charge density. They will have larger Lattice Enthalpies and larger
melting points because of the extra energy which must be put in to separate
the oppositely charged ions.
Units: kJ mol
-1
Cl Br F O
2-
Na
+
-780 -742 -918 -2478
K
+
-711 -679 -817 -2232
Rb
+
-685 -656 -783
Mg
2+
-2256 -3791
Ca
2+
-2259
Lattice Enthalpy Values
Smaller ions will have a greater attraction for each other because of their
higher charge density. They will have larger Lattice Enthalpies and larger
melting points because of the extra energy which must be put in to separate
the oppositely charged ions.
Cl
Na
+
Cl
The sodium ion has the same charge as a potassium ion but is smaller. It has a higher
charge density so will have a more effective attraction for the chloride ion. More energy
will be released when they come together.
K
+
Born-Haber Cycle For Sodium Chloride
kJ mol
-1
Enthalpy of formation of NaCl Na(s) + Cl
2
(g) > NaCl(s) 411
Enthalpy of sublimation of sodium Na(s) > Na(g) + 108
Enthalpy of atomisation of chlorine Cl
2
(g) > Cl(g) + 121
Ist Ionisation Energy of sodium Na(g) > Na
+
(g) + e + 500
Electron Affinity of chlorine Cl(g) + e > Cl(g) 364
Lattice Enthalpy of NaCl Na
+
(g) + Cl(g) > NaCl(s) ?
Born-Haber Cycle - NaCl
1
This is an exothermic process so
energy is released. Sodium
chloride has a lower enthalpy
than the elements which made it.
VALUE = - 411 kJ mol
-1
This is an exothermic process so
energy is released. Sodium
chloride has a lower enthalpy
than the elements which made it.
VALUE = - 411 kJ mol
-1
Na(s) + Cl
2
(g)
NaCl(s)
Enthalpy of formation of NaCl
Na(s) + Cl
2
(g) > NaCl(s)
1
1
2
This is an endothermic process.
Energy is needed to separate the
atoms. Sublimation involves
going directly from solid to gas.
VALUE = + 108 kJ mol
-1
This is an endothermic process.
Energy is needed to separate the
atoms. Sublimation involves
going directly from solid to gas.
VALUE = + 108 kJ mol
-1
Born-Haber Cycle - NaCl
Na(s) + Cl
2
(g)
NaCl(s)
Na(g) + Cl
2
(g)
Enthalpy of formation of NaCl
Na(s) + Cl
2
(g) > NaCl(s)
Enthalpy of sublimation of sodium
Na(s) > Na(g)
1
2
1
3
2
Breaking covalent bonds is an
endothermic process. Energy is
needed to overcome the
attraction the atomic nuclei have
for the shared pair of electrons.
VALUE = + 121 kJ mol
-1
Breaking covalent bonds is an
endothermic process. Energy is
needed to overcome the
attraction the atomic nuclei have
for the shared pair of electrons.
VALUE = + 121 kJ mol
-1
Born-Haber Cycle - NaCl
Na(s) + Cl
2
(g)
NaCl(s)
Na(g) + Cl
2
(g)
Na(g) + Cl(g)
Enthalpy of formation of NaCl
Na(s) + Cl
2
(g) > NaCl(s)
Enthalpy of sublimation of sodium
Na(s) > Na(g)
Enthalpy of atomisation of chlorine
Cl
2
(g) > Cl(g)
1
2
3
Born-Haber Cycle - NaCl
1
4
3
2
All Ionisation Energies are
endothermic. Energy is needed
to overcome the attraction the
protons in the nucleus have for
the electron being removed.
VALUE = + 500 kJ mol
-1
All Ionisation Energies are
endothermic. Energy is needed
to overcome the attraction the
protons in the nucleus have for
the electron being removed.
VALUE = + 500 kJ mol
-1
Na(s) + Cl
2
(g)
NaCl(s)
Na(g) + Cl
2
(g)
Na(g) + Cl(g)
Na
+
(g) + Cl(g)
Enthalpy of formation of NaCl
Na(s) + Cl
2
(g) > NaCl(s)
Enthalpy of sublimation of sodium
Na(s) > Na(g)
Enthalpy of atomisation of chlorine
Cl
2
(g) > Cl(g)
Ist Ionisation Energy of sodium
Na(g) > Na
+
(g) + e
1
2
3
4
Born-Haber Cycle - NaCl
1
5
4
3
2
Electron affinity is exothermic.
Energy is released as the nucleus
attracts an electron to the outer
shell of a chlorine atom.
VALUE = - 364 kJ mol
-1
Electron affinity is exothermic.
Energy is released as the nucleus
attracts an electron to the outer
shell of a chlorine atom.
VALUE = - 364 kJ mol
-1
Na(s) + Cl
2
(g)
NaCl(s)
Na(g) + Cl
2
(g)
Na(g) + Cl(g)
Na
+
(g) + Cl(g)
Na
+
(g) + Cl

(g)
Enthalpy of formation of NaCl
Na(s) + Cl
2
(g) > NaCl(s)
Enthalpy of sublimation of sodium
Na(s) > Na(g)
Enthalpy of atomisation of chlorine
Cl
2
(g) > Cl(g)
Ist Ionisation Energy of sodium
Na(g) > Na
+
(g) + e
Electron Affinity of chlorine
Cl(g) + e > Cl(g)
1
2
3
4
5
Born-Haber Cycle - NaCl
1
6
5
4
3
2
Na(s) + Cl
2
(g)
NaCl(s)
Na(g) + Cl
2
(g)
Na(g) + Cl(g)
Na
+
(g) + Cl(g)
Na
+
(g) + Cl

(g)
Enthalpy of formation of NaCl
Na(s) + Cl
2
(g) > NaCl(s)
Enthalpy of sublimation of sodium
Na(s) > Na(g)
Enthalpy of atomisation of chlorine
Cl
2
(g) > Cl(g)
Ist Ionisation Energy of sodium
Na(g) > Na
+
(g) + e
Electron Affinity of chlorine
Cl(g) + e > Cl(g)
Lattice Enthalpy of NaCl
Na
+
(g) + Cl(g) > NaCl(s)
1
2
3
4
5
6
Lattice Enthalpy is exothermic.
Oppositely charged ions are
attracted to each other.
Lattice Enthalpy is exothermic.
Oppositely charged ions are
attracted to each other.
Born-Haber Cycle - NaCl
1
6
5
4
3
2
Na(s) + Cl
2
(g)
NaCl(s)
Na(g) + Cl
2
(g)
Na(g) + Cl(g)
Na
+
(g) + Cl(g)
Na
+
(g) + Cl

(g)
CALCULATING THE LATTICE ENTHALPY
Apply Hesss Law
1
6
5
4 3 2 = - - - - +
The minus shows you are going in the
opposite direction to the definition
= - (-364) - (+500) - (+121) - (+108) + (-411)
= - 776 kJ mol
-1
Born-Haber Cycle - NaCl
1
6
5
4
3
2
Na(s) + Cl
2
(g)
NaCl(s)
Na(g) + Cl
2
(g)
Na(g) + Cl(g)
Na
+
(g) + Cl(g)
Na
+
(g) + Cl

(g)
CALCULATING THE LATTICE ENTHALPY
Apply Hesss Law
1
6
5
4 3 2 = - - - - +
The minus shows you are going in the
opposite direction to the definition
= - (-364) - (+500) - (+121) - (+108) + (-411)
= - 776 kJ mol
-1
OR
Ignore the signs and just use the values;
If you go up you add, if you come down
you subtract the value
= - - - -
= (364) - (500) - (121) - (108) - (411)
= - 776 kJ mol
-1
1 6 5 4 3 2
1
6
5
4
3
2
Mg(s) + Cl
2
(g)
MgCl
2
(s)
Mg(g) + Cl
2
(g)
Mg(g) + 2Cl(g)
Mg
2+
(g) + 2Cl

(g)
7
Mg
+
(g) + 2Cl(g)
Mg
2+
(g) + 2Cl(g)
Enthalpy of formation of MgCl
2
Mg(s) + Cl
2
(g) > MgCl
2
(s)
Enthalpy of sublimation of magnesium
Mg(s) > Mg(g)
Enthalpy of atomisation of chlorine
Cl
2
(g) > Cl(g) x2
Ist Ionisation Energy of magnesium
Mg(g) > Mg
+
(g) + e
2nd Ionisation Energy of magnesium
Mg
+
(g) > Mg
2+
(g) + e
Electron Affinity of chlorine
Cl(g) + e > Cl(g) x2
Lattice Enthalpy of MgCl
2
Mg
2+
(g) + 2Cl(g) > MgCl
2
(s)
1
2
3
4
5
7
6
Born-Haber Cycle - MgCl
2
BORN-HABER
CYCLES
THE END
KNOCKHARDY PUBLISHING